Fenton试剂协同TiO_2光催化降解三氯乙酸及协同机理

为了研究Fenton试剂协同TiO2光催化降解三氯乙酸(TCAA)的反应及其协同机理,在自制的光催化反应装置中分别考察了Fenton、UV/TiO2及Fenton/UV/TiO23个反应对TCAA的降解情况。研究结果表明,在TCAA初始浓度为2.0 mg/L,TiO2用量为1.0 g/L,紫外辐射光源为15 W(λmain=254 nm)的实验条件下,Fenton试剂协同TiO2光催化降解TCAA反应在pH 3~7范围内均有较高的降解率;TCAA在Fenton、UV/TiO2及Fenton/UV/TiO23个反应中的一级反应速率常数分别为0.0009、0.0131和0.0456 min-1;Fenton试剂与TiO2光催化反应间存在较明显的协同效应,其协同机理主要体现在两个方面:一是紫外光激发Fe(OH)2+和H2O2分解产生更多的·OH,二是Fenton试剂中部分被氧化成的Fe3+可与TiO2表面的光生电子结合被还原为Fe2+,抑制了光生电子与空穴的复合,从而提高了TiO2光催化降解TCAA的效率。     

FeAlOx/MMT催化Fenton反应降解高浓度苯酚废水

以蒙脱土为载体制备负载型Fe/Al复合氧化物(FeAlOx/MMT)用于催化Fenton反应降解高浓度苯酚废水。实验结果表明,活性相FeAlOx中Fe/Al摩尔比为0.22时制备所得催化剂对Fenton反应具有最佳活性,且Fe/Al复合氧化物并未嵌入蒙脱土层间。在低温和高pH条件下催化体系存在诱导期,诱导期内FeAlOx/MMT缓释出Fe离子并进而由Fe离子催化溶液中的Fenton反应。通过对非均相催化降解苯酚废水的动力学研究发现,H2O2初始浓度、溶液的pH和反应温度对COD降解效率具有显著影响。调节降解过程中的温度序列和氧化剂引入程序能够缓解高温和高双氧水浓度双重因素耦合导致的HO.自消耗。在优化的降解条件下使用理论用量的H2O2可使得1 g/L的苯酚废水中苯酚降解率达到100%,而COD的降解率则达到97%。     

FeAlO_x/MMT催化Fenton反应降解高浓度苯酚废水

以蒙脱土为载体制备负载型Fe/Al复合氧化物（FeAlOx/MMT）用于催化Fenton反应降解高浓度苯酚废水。实验结果表明,活性相FeAlOx中Fe/Al摩尔比为0.22时制备所得催化剂对Fenton反应具有最佳活性,且Fe/Al复合氧化物并未嵌入蒙脱土层间。在低温和高pH条件下催化体系存在诱导期,诱导期内FeAlOx/MMT缓释出Fe离子并进而由Fe离子催化溶液中的Fenton反应。通过对非均相催化降解苯酚废水的动力学研究发现,H2O2初始浓度、溶液的pH和反应温度对COD降解效率具有显著影响。调节降解过程中的温度序列和氧化剂引入程序能够缓解高温和高双氧水浓度双重因素耦合导致的HO.自消耗。在优化的降解条件下使用理论用量的H2O2可使得1 g/L的苯酚废水中苯酚降解率达到100%,而COD的降解率则达到97%。     

固定化催化剂TiO2膜光催化降解三氯乙醛的研究

研究了负载于玻璃上的固定化催化剂TiO2膜光催化降解水中三氯乙醛的效果,探讨了TiO2膜光催化降解三氯乙醛的机理,考察了溶液pH值和三氯乙醛初始浓度埘TiO2膜光催化降解三氯乙醛的影响,并研究了固定化催化剂TiO2膜光催化降解三氯乙醛的动力学.结果表明,固定化催化剂TiO2膜光催化降解水中三氯乙醛的效果良好,当三氯乙醛初始浓度为2.25 mg/L时,在紫外光照时间3 h下,三氯乙醛的降解率高达100%.在相司紫外光照时间下,三氯乙醛的光催化降解率随着三氯乙醛初始浓度的增大而下降.在溶液pH=6.5时,三氯乙醛的降解效率最高.固定化催化剂TiO2膜光催化降解三氯乙醛的反应遵循一级反应动力学,反应速率常数随三氯乙醛初始浓度的增大而减小.     

负载型TiO2固定相光催化降解含酚废水的试验研究

以20W紫外灯为光源,研究了将TiO2粉末负载在硅胶颗粒上,对含酚废水进行光催化降解.由试验得出光催化反应过程中的工艺条件,在此基础上添加H2O2、Fe3+、Cu2+,反应1 h后,苯酚的降解率达95%以上.     

磷钨酸光催化降解甲基橙溶液的研究

以磷钨酸为光催化剂,在紫外灯照射下,对模拟染料废水甲基橙溶液进行光催化降解,并研究了催化剂加入量、pH值、甲基橙初始浓度和外加氧化剂H2O2对光催化降解效果的影响.结果表明,磷钨酸光催化剂加入量为300 mg/100 mL,pH=2.5时,甲基橙溶液的降解率明显高于其他pH值的降解率;在较低浓度下,甲基橙溶液的光催化降解反应符合一级动力学方程;外加氧化剂H2O2可提高光催化反应速率.     

磷钨酸光催化降解甲基橙溶液的研究

以磷钨酸为光催化刺，在紫外灯照射下。对模拟染料废水甲基橙溶液进行光催化降解，并研究了催化剂加入量、pH值、甲基橙初始浓度和外加氧化剂H2O2对光催化降解效果的影响。结果表明，磷钨酸光催化剂加入量为300mg／100mL，pH=2．5时，甲基橙溶液的降解率明显高于其他pH值的降解率；在较低浓度下，甲基橙溶液的光催化降解反应符合一级动力学方程；外加氧化剂H2O2可提高光催化反应速率。     

Fe~(3+)掺杂TiO_2/凹凸棒复合材料的光催化性能

采用酸催化的溶胶-凝胶法制备了一系列Fe3+掺杂TiO2/凹凸棒(Fe3+-TiO2/ATP)复合光催化剂材料。在可见光条件下,以亚甲基蓝(MB)溶液的光催化降解反应,评价了样品的光催化性能,研究了TiO2负载量、Fe3+掺杂量和焙烧温度对复合材料光催化性能的影响。在单因素实验的基础上,采用正交实验设计(L25(53))优化了催化剂的制备条件。光催化实验结果表明,MB在复合材料上的光催化降解反应遵循Langmuir-Hinshelwood(L-H)动力学模型。正交实验结果表明,当TiO2负载量为15%、Fe3+掺杂量为0.5%和焙烧温度为550℃时,得到的复合材料对MB的光催化降解效率最佳,测得表观反应速率常数kapp为6.09×10-3min-1,反应4 h后MB的降解率(Dt)可达75.88%,相同实验条件下与P25(1.51×10-3min-1)相比较,反应速率提高了4.03倍,降解率提高了45.05%。另外,复合材料的沉降性能优于P25,易于分离,是一类有应用前景的复合光催化剂。     

光助Fenton氧化法降解水中六氯苯的研究

采用光助Fenton氧化法处理六氯苯模拟废水,考察了反应时间、Fe3 与H2O2摩尔比、Fenton试剂用量、初始pH、六氯苯初始浓度、光强对六氯苯降解效果的影响,并初步探讨了六氯苯的降解动力学规律.结果表明.光助Fenton法降解六氯苯的最佳工艺条件为:紫外灯功率为300 W、Fe3 投加量为1.0 mmol/L、H2O2投加量为5.0 mmol/L、反应时间为60 min、初始pH为3,在此条件下,浓度为500μg/L的HCB的去除率可达91.3%.UV辐射与Fenton氧化对HCB的降解具有协同效应.光助Fenton法对HCB的降解符合一级反应动力学方程,表观速率常数为0.04 min-1,与Fenton法相比,提高了近9倍.     

二氧化钛纳米管光催化降解水中百草枯

二氧化钛纳米管被用于光催化氧化水体中的百草枯,对光催化反应条件、常见Fe3+离子的干扰情况和百草枯光催化降解动力学规律进行了研究。结果表明,浓度为25 mg/L的百草枯溶液,在二氧化钛纳米管(TNT)1.0 g/L,H2O20.5 mL/50 mL,pH=5.0的最优光催化氧化条件下,经过30 min反应可以被100%从水体中去除,表现出非常高的光催化降解效率;动力学方程拟合表明,百草枯光催化氧化反应符合拟一级动力学规律,动力学方程为ln(C0/C)=1.0267t-0.1282,反应速率常数K为1.0267 h-1;双氧水存在时常见的Fe3+能够进一步提高百草枯光催化降解率;该光催化反应体系对低浓度百草枯废水有很好的处理效果,预示着光催化氧化技术适合地表或地下水体中百草枯的去除。     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Radionuclides and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.     

Radionuclides in deer and elk from Los Alamos national laboratory and the doses to humans from the ingestion of muscle and bone

Abstract

This paper summarizes radionuclide concentrations (³H, ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu, ²⁴¹Am, and ^totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p<0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% on LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y^‐1 (2.2 μSv y^‐1), deer bone = 3.8 mrem y^‐1 (38 μSv y^‐1), elk muscle = 0.12 mrem y^‐1 (1.2 μSv y^‐1), and elk bone = 1.7 mrem y^‐1 (17 μSv y^‐1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y^‐1 (1000 μSv y^‐1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E‐06, which is far below the Environmental Protection Agency upper level guideline of 1E‐04.     

Radionuclides in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.